JP2018131673A - Sputtering deposition apparatus and method, and method for manufacturing laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sputtering deposition apparatus and the like, capable of performing reactive sputtering for long time.SOLUTION: In a film deposition apparatus having at least one film deposition means constituted of reactive multitarget sputtering deposition means, the sputtering deposition means comprises: a cathode box 212 having first and second cathode chambers 601 and 602 partitioned by a partition plate 214; a first target (Cu) and a second target (Ni) mounted on sputtering cathode 202 and 203 stored in each cathode chamber; and means 206 for supplying Ar gas into the first cathode chamber and means 207 and 208 for supplying Ar gas including reactive gas (O), water and the like into the second cathode chamber. Cu target particles flying from the first cathode chamber merges with Ni target particles flying from the second cathode chamber in the top direction of the partition plate in a space region in the vicinity of a can roll 200 to deposit a reactive multitarget sputtering film.SELECTED DRAWING: Figure 10

Description

  The present invention relates to a sputtering film forming apparatus, a sputtering film forming method, and a laminate film manufacturing method, and more particularly, to a sputtering film forming apparatus, a sputtering film forming method, and The present invention relates to an improvement in a method for producing a laminate film.

  As a material for electrode substrate films used in liquid crystal panels, notebook computers, mobile phones, touch panels, etc., conventionally, a transparent substrate (resin film) and a laminated film formed on this substrate (consisting of a metal absorption layer and a metal layer) ) Is used.

  The metal absorption layer is usually composed of a metal oxide film or a metal nitride film, and a sputtering method is widely used as a method for producing a laminate film.

  In addition, when an oxide target or a nitride target is used to form the metal absorption layer, the film formation rate may be slowed to reduce productivity. Reactive sputtering using an alloy target (for example, a target such as a CuNi alloy) and introducing a reactive gas (oxygen gas or nitrogen gas) into a vacuum chamber is employed.

  By the way, a metal absorption layer made of a metal oxide film is continuously formed on the surface of a long resin film by reactive sputtering using a target such as a CuNi alloy and a reactive gas (oxygen gas), and copper is formed on the metal absorption layer. When the above-mentioned electrode substrate film was produced using a laminate film produced by continuously forming a metal layer by sputtering using a target such as the above, the following problems existed.

  That is, when a laminated film (metal absorption layer and metal layer) of the above-mentioned laminate film is etched to produce an electrode substrate film, the film formation start side lamination in which the metal absorption layer is formed in the initial stage of continuous film formation Compared with the body film, the etching property is inferior when the film-forming end side laminate film in which the metal absorption layer is formed in the final stage of continuous film formation, resulting in the circuit pattern in the electrode substrate film. There was a problem that the machining accuracy of was not stable.

  Regarding the problem of poor etching properties when the above-mentioned film formation termination side laminate film (laminate film in which a metal absorption layer is formed at the final stage of continuous film formation) is applied, in Patent Document 1 and Patent Document 2, As a cause, the time-dependent change of the film forming environment in reactive sputtering (the time-dependent change of residual moisture in the vacuum chamber) is predicted, and the following solution method is proposed.

  That is, when forming a metal absorption layer (metal oxide film) by reactive sputtering using a target such as a CuNi alloy and a reactive gas (oxygen gas), in Patent Document 1, water is included in the reactive gas. A method for forming a metal absorption layer (metal oxide film) while compensating for the decrease in the amount of moisture in the vacuum chamber is proposed. In Patent Document 2, hydrogen is included in the reactive gas to provide the amount of moisture in the vacuum chamber. Has proposed a method of forming a metal absorption layer (metal oxide film) while compensating for the decrease in the thickness.

  And the etching property of the laminated film in the said laminated body film is improved by employ | adopting each method proposed by patent document 1 and patent document 2. FIG.

  FIG. 5 shows a sputtering film forming apparatus (sputtering web coater) described in Patent Document 1 and Patent Document 2 that forms a metal absorption layer (metal oxide film) while compensating for the reduced amount of moisture in the vacuum chamber. Further, magnetron sputtering cathodes 17, 18, 19 and 20 as film forming means are disposed on the opposite side of the cooling can roll 16 which conveys the long resin film 12 in contact with the surface, and these magnetron sputtering cathodes 17 are provided. , 18, 19, 20, gas supply pipes 25, 26, 27, 28, 29, which discharge a mixed gas of a reactive gas (oxygen gas) containing water or the like and a process gas (argon gas or the like), 30, 31 and 32 are attached.

  The sputtering film forming apparatus (sputtering web coater) shown in FIG. 5 has a structure using magnetron sputtering cathodes 17, 18, 19, and 20 on which a plate-like target (not shown) is mounted. When the target is plate-shaped, there is a drawback that a non-erosion region (a region in which the following particle deposit is involved) is formed on the target surface. For this reason, as shown in FIG. 6, cylindrical magnetron sputtering cathodes 117, 118, 119, and 120 on which a rotary target (not shown) in which a non-erosion region is not formed on the surface are mounted may be applied.

WO 2016/084605 A1 publication WO 2016/067943 A1 publication

J. et al. Vac. Soc. Jpn. Vol. 53, no. 9, (2010), p515-520

  By the way, a continuous metal absorption layer (metal oxide film) is formed by a reactive sputtering method using a sputtering film forming apparatus (sputtering web coater) shown in FIGS. 5 and 6 in which an alloy target made of a CuNi alloy or the like is mounted on a sputtering cathode. When film formation is performed, a compound produced by a reaction between the reactive gas (oxygen gas) and the alloy target is deposited as a particle deposit on the non-erosion region of the alloy target, and further, at the end of the erosion region of the alloy target. It is known that foreign matters called nodules are generated.

  If particle deposits are deposited in the non-erosion region and nodules are generated at the end of the erosion region, there is a problem that the subsequent reactive sputtering is hindered. This was remarkable when the sputtering power or the input current (sputtering current) was set high.

  The present invention has been made paying attention to such problems, and the problem is that, for example, a metal absorption layer (metal oxide film) is continuously formed by reactive sputtering using a reactive gas (oxygen gas). An object of the present invention is to provide a sputtering film-forming apparatus, a sputtering film-forming method, and a method for producing a laminated film, which enable stable reactive sputtering film formation for a long time even when the film is formed.

  As a result of continual research by the inventor in order to solve the above problems, the following technical knowledge has been obtained.

  First, in the methods of Patent Documents 1 and 2, a metal absorption layer (metal oxide film) is formed using an alloy target made of a CuNi alloy or the like and a reactive gas (oxygen gas). It was confirmed that Ni was more dominant than Cu in the oxidation of CuNi alloy by Cu. That is, in reactive sputtering using an alloy target and a reactive gas (oxygen gas), since oxidation of Ni is more dominant than Cu, the oxidation of Cu hardly occurs. There was a great waste of power input (sputtering power).

  In addition, when a metal absorption layer (metal oxide film) is formed using an alloy target made of CuNi alloy or the like and a reactive gas (oxygen gas), it is difficult to oxidize Cu. It was also confirmed that particle deposits were easily deposited in the non-erosion region of the alloy target.

  Therefore, instead of the conventional reactive sputtering method using an alloy target made of a CuNi alloy or the like, the reactive multi-source sputtering film forming method divided into “Cu target” and “addition metal (for example, Ni) target” other than Cu. Attempting to hire them led to the discovery that the above problems could be solved.

That is, the first invention according to the present invention is:
A cooling can roll that conveys a long body in contact with the surface, and a plurality of sputtering film forming means arranged opposite to the surface of the cooling can roll are provided in a vacuum chamber, and the sputtering film forming means In the sputtering film forming apparatus in which a thin film is formed on the surface of the elongated body conveyed through the gap with the cooling can roll, and at least one of the sputtering film forming means is constituted by a reactive multi-source sputtering film forming means,
The reactive multi-source sputtering film forming means is accommodated in a cathode box having a cooling can roll side open, a first cathode chamber and a second cathode chamber partitioned by a partition plate in the cathode box, and the first cathode chamber. And a second sputtering cathode housed in the first sputtering cathode and the second cathode chamber to which the first target is mounted and a second target is mounted, a gas supply means for supplying a process gas into the first cathode chamber, and A first target that is provided with a gas supply means for supplying a process gas containing a reactive gas in the second cathode chamber and that comes from the first cathode chamber in the space region in the direction of the tip of the partition plate and in the vicinity of the cooling can roll. Combine the particles and the second target particles flying from the second cathode chamber It is characterized in that the reactive multi-source sputtering deposition is performed.

Further, the second invention according to the present invention is:
In the sputtering film forming apparatus according to the first invention,
The first sputtering cathode and the second sputtering cathode are constituted by a magnetron sputtering cathode in which a plurality of magnets are fixedly arranged, and the normal line at the center of the surface of each magnet facing the cooling can roll is a cooling can. It is characterized in that it intersects at the approximate center of the space area in the vicinity of the roll,
The third invention is
In the sputtering film forming apparatus according to the first invention or the second invention,
The second sputtering cathode on which the second target is mounted is composed of a cylindrical magnetron sputtering cathode, and the second target is composed of a rotary target,
The fourth invention is:
In the sputtering film forming apparatus according to the first invention,
A shielding mask having an opening is disposed at a position near the cooling can roll of the cathode box, and an opening of the shielding mask is aligned with the space area near the cooling can roll. .

Next, the fifth invention according to the present invention is:
The long body is transported while being held in contact with the surface of the cooling can roll provided in the vacuum chamber, and a thin film is formed on the surface of the long body by a plurality of sputtering film forming means arranged to face the cooling can roll surface. In a sputtering film forming method comprising: forming and forming at least one of the sputtering film forming means by a reactive multi-source sputtering film forming means;
The reactive multi-source sputtering film forming means is accommodated in the cathode box opened on the cooling can roll side, the first cathode chamber and the second cathode chamber partitioned by the partition plate in the cathode box, and the first cathode chamber. And a second sputtering cathode housed in the first sputtering cathode and the second cathode chamber to which the first target is mounted and a second target is mounted, a gas supply means for supplying a process gas into the first cathode chamber, and A first target that is provided with a gas supply means for supplying a process gas containing a reactive gas in the second cathode chamber and that comes from the first cathode chamber in the space region in the direction of the tip of the partition plate and in the vicinity of the cooling can roll. Combine the particles and the second target particles flying from the second cathode chamber And performing a reactive multi-source sputtering deposition.

In addition, the sixth invention,
In the sputtering film forming method according to the fifth invention,
The first sputtering cathode and the second sputtering cathode are configured by a magnetron sputtering cathode in which a plurality of magnets are fixedly arranged, and the normal line at the center of the surface of each magnet facing the cooling can roll is a cooling can. It is characterized by intersecting at the approximate center of the space area in the vicinity of the roll,
The seventh invention
In the sputtering film forming method according to the fifth invention or the sixth invention,
The second sputtering cathode on which the second target is mounted is constituted by a cylindrical magnetron sputtering cathode, and the second target is constituted by a rotary target,
The eighth invention
In the sputtering film forming method according to the fifth invention,
The reactive gas is oxygen gas or nitrogen gas,
The ninth invention
In the sputtering film forming method according to the fifth invention or the eighth invention,
The reactive gas is composed of oxygen gas, and the reactive gas contains water or hydrogen,
The tenth invention is
In the sputtering film forming method according to the fifth invention,
The first target accommodated in the first cathode chamber is constituted by a copper target, and the second target accommodated in the second cathode chamber is constituted by a metal target for addition other than copper,
The eleventh invention is
In the sputtering film forming method according to the tenth invention,
The additive metal target is composed of one or more metals selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Mn, Ni, Co, and Zn,
The twelfth invention
In the sputtering film forming method according to the eleventh invention,
By adjusting the input power or input current to the first sputtering cathode and the second sputtering cathode, a copper alloy thin film in which the mixing ratio of the additive metal to copper is 3 to 40% is formed. is there.

Next, a thirteenth aspect of the present invention is:
It is composed of a long body made of a transparent resin film and a laminated film formed on at least one side of the long body, and the laminated film is a first metal absorption layer counted from the long body side, In the manufacturing method of the laminated body film which has the copper layer of the 2nd layer and the metal absorption layer of the 3rd layer,
The first metal absorption layer and the third metal absorption layer are formed by the sputtering film forming method according to any one of the fifth to twelfth inventions,
The fourteenth invention is
In the method for producing a laminate film according to the thirteenth invention,
The thicknesses of the first metal absorption layer and the third metal absorption layer are set in a range of 15 nm to 30 nm.

According to the sputtering film forming apparatus and the sputtering film forming method of the present invention,
At least one of the sputtering film forming means is constituted by a reactive multi-source sputtering film forming means, and
The reactive multi-source sputtering film forming means is accommodated in the cathode box opened on the cooling can roll side, the first cathode chamber and the second cathode chamber partitioned by the partition plate in the cathode box, and the first cathode chamber. And a second sputtering cathode housed in the first sputtering cathode and the second cathode chamber to which the first target is mounted and a second target is mounted, a gas supply means for supplying a process gas into the first cathode chamber, and A gas supply means for supplying a process gas containing a reactive gas in the second cathode chamber;
Reactive multi-source sputtering film formation is performed by merging the first target particles flying from the first cathode chamber and the second target particles flying from the second cathode chamber in the space region near the front end of the partition plate and in the vicinity of the cooling can roll. It is characterized by doing.

  A target that easily reacts with the reactive gas (second target) is attached to the second sputtering cathode, and a target that is less reactive with the reactive gas than the second target (first target) is attached to the first sputtering cathode. By doing so, the input power (or input current) to each sputtering cathode can be set to a value suitable for the target to be mounted, and the first target is not supplied with reactive gas in the first cathode chamber. It is also possible to prevent the generation of particle deposits on the surface.

  Therefore, compared to the conventional method in which the input power (or input current) to the sputtering cathode equipped with the alloy target is set high, the waste of input power (or input current) is eliminated, and the input power to the sputtering cathode is eliminated. Since the (or input current) can be set lower than before, it is possible to prevent the above-described generation of particle deposits, nodules and the like.

The schematic cross-section explanatory drawing of the laminated body film which has a 1st metal absorption layer and a 2nd metal layer counting from the transparent substrate side on both surfaces of the transparent substrate which consists of a resin film. The first metal absorption layer and the second metal layer are counted on both sides of the transparent substrate made of a resin film from the transparent substrate side, and the metal layer is formed by a dry film formation method and a wet film formation method. The schematic cross-section explanatory drawing of the laminated body film. The first metal absorption layer, the second metal layer and the third metal absorption layer counted from the transparent substrate side on both sides of the transparent substrate made of a resin film, and the metal layer is dry-type Schematic cross-sectional explanatory drawing of the laminated body film formed with the film-forming method and the wet film-forming method. The schematic cross-section explanatory drawing of the electrode substrate film in which the metal lamination | stacking thin wire | line was formed in both surfaces of the transparent substrate which consists of a resin film, respectively. Structure explanatory drawing of the sputtering film-forming apparatus which concerns on the patent document 1 and the patent document 2 incorporating the sputtering cathode with which the plate-shaped target was mounted | worn. Structure explanatory drawing of the sputtering film-forming apparatus which concerns on patent document 1 and patent document 2 incorporating the sputtering cathode with which the rotary target was mounted | worn. The elements on larger scale of the sputtering film-forming apparatus which concerns on this invention. The relationship between the film formation time (seconds) during the moisture pressure control and the H ₂ O flow rate (sccm) in the vacuum chamber, and the relationship between the film formation time (seconds) and H ₂ O / Ar in the vacuum chamber, respectively. FIG. The elements on larger scale of the sputtering film-forming apparatus which concerns on a comparative example. The enlarged view of the cathode box in the sputtering film-forming apparatus shown in FIG.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

(1) Laminate film (1-1) First laminate film The first laminate film is composed of a transparent substrate 40 made of a resin film as shown in FIG. The metal absorption layers 41 and 43 and the metal layers 42 and 44 formed by the method (sputtering method) are used.

  The metal layer may be formed by a combination of a dry film formation method (sputtering method) and a wet film formation method (wet plating method).

  That is, as shown in FIG. 2, a transparent substrate 50 made of a resin film, and metal absorption layers 51 and 53 with a film thickness of 15 nm to 30 nm formed on both surfaces of the transparent substrate 50 by a dry film forming method (sputtering method); Metal layers 52 and 54 formed on the metal absorption layers 51 and 53 by a dry film formation method (sputtering method), and metals formed on the metal layers 52 and 54 by a wet film formation method (wet plating method) You may comprise with the layers 55 and 56. FIG.

(1-2) Second Laminate Film Next, the second laminate film is premised on the first laminate film shown in FIG. 2, and the second metal absorption on the metal layer of the laminate film. A layer is formed.

  That is, as shown in FIG. 3, a transparent substrate 60 made of a resin film, and metal absorption layers 61 and 63 having a film thickness of 15 nm to 30 nm formed on both surfaces of the transparent substrate 60 by a dry film forming method (sputtering method); Metal layers 62 and 64 formed on the metal absorption layers 61 and 63 by a dry film formation method (sputtering method), and metal formed on the metal layers 62 and 64 by a wet film formation method (wet plating method) The layers 65 and 66 and the second metal absorption layers 67 and 68 having a film thickness of 15 nm to 30 nm formed on the metal layers 65 and 66 by a dry film forming method (sputtering method).

  Here, in the second laminate film shown in FIG. 3, the metal absorbing layer 61 and the second metal absorbing layer 67 are formed on both surfaces of the metal layers denoted by reference numerals 62 and 65, and the metals denoted by reference numerals 64 and 66 are formed. The metal absorption layer 63 and the second metal absorption layer 68 are formed on both sides of the layer because the mesh made of the metal laminated thin wires when the electrode substrate film produced using the laminate film is incorporated in the touch panel. This is to prevent the circuit pattern of the structure from being reflected.

  Even when an electrode substrate film is formed using a first laminate film in which a metal absorption layer is formed on one side of a transparent substrate made of a resin film and the metal layer is formed on the metal absorption layer, It is possible to prevent the circuit pattern from being visually recognized from the transparent substrate.

(1-3) Metal Absorption Layer The metal absorption layer is a reactive multiple using a reactive gas (oxygen gas) using a Cu target (first target) and an additional metal target (second target) other than copper. It is preferable to use a Cu-based alloy formed by sputtering.

  The additive metal target (second target) is composed of one or more metals selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Mn, Ni, Co, and Zn. be able to.

(1-4) Metal layer The material constituting the metal layer is not particularly limited as long as the metal has a low electrical resistance value. For example, Cu alone, Ti, Al, V, W, Ta, Si, Cr Cu-based alloy to which one or more elements selected from Ag are added, or Ag alone, or one or more elements selected from Ti, Al, V, W, Ta, Si, Cr, Cu are added In particular, Cu alone is desirable from the viewpoint of the workability of the circuit pattern and the resistance value.

  The thickness of the metal layer depends on the electrical characteristics and is not determined from optical elements, but is usually set to a thickness at which transmitted light cannot be measured.

(1-5) Resin film constituting transparent substrate The material of the resin film applied to the laminate film is not particularly limited. Specific examples thereof include polyethylene terephthalate (PET), polyethersulfone (PES). ), Polyarylate (PAR), polycarbonate (PC), polyolefin (PO), triacetylcellulose (TAC) and norbornene resin material alone, or resin film alone selected from the above resin materials And an acrylic organic film covering one side or both sides of the single body. In particular, as for norbornene resin materials, representative examples include ZEONOR (trade name) manufactured by ZEON Corporation, Arton (trade name) manufactured by JSR Corporation, and the like.

  In addition, since the following electrode substrate film produced using a laminated body film is used for a touch panel etc., what is excellent in transparency in a visible wavelength region among resin films is desirable.

(2) Electrode substrate film (2-1) An electrode substrate film used for liquid crystal panels, notebook computers, mobile phones, touch panels, etc. is obtained by etching and processing the laminated film of the laminate film. Can do. Specifically, an electrode substrate film as shown in FIG. 4 can be obtained by etching the laminate film of the laminate film shown in FIG.

  That is, the electrode substrate film shown in FIG. 4 has a circuit pattern having a mesh structure composed of a transparent substrate 70 made of a resin film and metal laminated thin wires provided on both surfaces of the transparent substrate 70. Counting from the transparent substrate 70 side, the first metal absorbing layers 71, 73, the second metal layers 72, 75, 74, 76, the third metal absorbing layer 77, 78.

  And it can use for a touch panel by making the electrode (wiring) pattern of an electrode substrate film into the stripe form or grid | lattice form for touch panels. Moreover, since the metal laminated thin wire processed into the electrode (wiring) pattern maintains the laminated structure of the laminate film, the circuit pattern such as the electrode provided on the transparent substrate even under high-luminance illumination It can be provided as an electrode substrate film that is extremely difficult to be visually recognized.

(2-2) And wiring processing from the laminate film to the electrode substrate film can be performed by a known subtractive method. In the subtractive method, a photoresist film is formed on the laminate film surface of the laminate film, exposed and developed so that the photoresist film remains at a position where a wiring pattern is to be formed, and the photoresist film is formed on the laminate film surface. This is a method of forming a wiring pattern by removing a laminated film at a location that does not exist by chemical etching.

  As an etching solution for chemical etching, for example, a ferric chloride aqueous solution or a cupric chloride aqueous solution can be used.

(3) Sputtering film forming apparatus described in Patent Documents 1 and 2 (3-1) Sputtering film forming apparatus equipped with a plate-like target The conventional sputtering film forming apparatus described in Patent Documents 1 and 2 5 is provided in the vacuum chamber 10, and after performing a predetermined film forming process on the long resin film (long body) 12 unwound from the unwinding roll 11, the winding roll 24 is wound up. A cooling can roll 16 that is rotationally driven by a motor is disposed in the middle of the conveyance path from the unwinding roll 11 to the winding roll 24. A coolant whose temperature is adjusted outside the vacuum chamber 10 circulates inside the can roll 16.

In the vacuum chamber 10, for the sputtering film formation, the pressure is reduced to an ultimate pressure of about 10 ⁻⁴ Pa and the pressure is adjusted to about 0.1 to 10 Pa by introducing a process gas (sputtering gas) thereafter. A known gas such as argon is used as the process gas, and a reactive gas (oxygen gas) is further added. The shape and material of the vacuum chamber 10 are not particularly limited as long as they can withstand such a reduced pressure state, and various types can be used. In order to maintain the vacuum chamber 10 under reduced pressure, various devices (not shown) such as a dry pump, a turbo molecular pump, and a cryocoil are incorporated in the vacuum chamber 10.

  A free roll 13 for guiding the long resin film 12 and a tension sensor roll 14 for measuring the tension of the long resin film 12 are arranged in this order on the transport path from the unwinding roll 11 to the can roll 16. Yes. The long resin film 12 fed from the tension sensor roll 14 toward the can roll 16 is adjusted with respect to the peripheral speed of the can roll 16 by a motor-driven front feed roll 15 provided in the vicinity of the can roll 16. Thus, the long resin film 12 can be brought into close contact with the outer peripheral surface of the can roll 16.

  Similarly to the above, the conveyance path from the can roll 16 to the take-up roll 24 is a motor driven post-feed roll 21 that adjusts the peripheral speed of the can roll 16 and a tension sensor roll that measures the tension of the long resin film 12. 22 and a free roll 23 for guiding the long resin film 12 are arranged in this order.

  In the unwinding roll 11 and the winding roll 24, the tension balance of the long resin film 12 is maintained by torque control using a powder clutch or the like. In addition, the long resin film 12 is unwound from the unwinding roll 11 and wound around the winding roll 24 by the rotation of the can roll 16 and the motor-driven front feed roll 15 and the rear feed roll 21 that rotate in conjunction with the rotation. It has come to be taken.

  In the vicinity of the can roll 16, as a film forming means, at a position facing a conveyance path defined on the outer peripheral surface of the can roll 16 (a region where the long resin film 12 in the outer peripheral surface of the can roll 16 is wound). Magnetron sputtering cathodes 17, 18, 19, and 20 on which sputtering targets are respectively mounted are disposed, and reactive gas containing water or the like as described above in the vicinity of these magnetron sputtering cathodes 17, 18, 19, 20. Gas supply pipes 25, 26, 27, 28, 29, 30, 31, and 32 for releasing a mixed gas of (oxygen gas) and process gas (argon gas or the like) are provided.

  When the metal layer is formed using the magnetron sputtering cathodes 19 and 20, the reactive gas (oxygen) is supplied from the gas supply pipes 29, 30, 31, and 32 provided in the vicinity of the magnetron sputtering cathodes 19 and 20. Gas) is not supplied, but process gas (argon gas or the like) is supplied.

(3-2) Sputtering film forming apparatus equipped with a rotary target In the sputtering film forming apparatus shown in FIG. 5, a magnetron sputtering cathode equipped with a plate-like target is incorporated. In addition, there is a drawback that a non-erosion region is formed on the target surface. For this reason, as shown in FIG. 6, cylindrical magnetron sputtering cathodes 117, 118, 119, and 120 for mounting a rotary target (not shown) in which a non-erosion region is not formed on the surface may be incorporated.

  That is, a conventional sputtering film forming apparatus incorporating a cylindrical magnetron sputtering cathode equipped with a rotary target is provided in a vacuum chamber 110 as shown in FIG. A predetermined film forming process is performed on the long resin film 112 (long body), and then the film is wound by a winding roll 124. A cooling can roll 116 that is rotationally driven by a motor is disposed in the middle of the conveyance path from the unwind roll 111 to the take-up roll 124. Inside the can roll 116, a coolant whose temperature is adjusted outside the vacuum chamber 110 circulates.

In the vacuum chamber 110, because of sputtering film formation, pressure reduction to an ultimate pressure of about 10 ⁻⁴ Pa and subsequent pressure adjustment by about 0.1 to 10 Pa by introduction of a process gas are performed. A known gas such as argon is used as the process gas, and a reactive gas (oxygen gas) is further added. The shape and material of the vacuum chamber 110 are not particularly limited as long as they can withstand such a reduced pressure state, and various types can be used. In order to maintain the vacuum chamber 110 under reduced pressure, various devices (not shown) such as a dry pump, a turbo molecular pump, and a cryocoil are incorporated in the vacuum chamber 110.

  A free roll 113 for guiding the long resin film 112 and a tension sensor roll 114 for measuring the tension of the long resin film 112 are arranged in this order on the transport path from the unwinding roll 111 to the can roll 116. Yes. Further, the long resin film 112 sent from the tension sensor roll 114 toward the can roll 116 is adjusted with respect to the peripheral speed of the can roll 116 by a motor-driven front feed roll 115 provided in the vicinity of the can roll 116. Thus, the long resin film 112 can be brought into close contact with the outer peripheral surface of the can roll 116.

  Similarly to the above, the conveyance path from the can roll 116 to the take-up roll 124 is a motor-driven feed roll 121 that adjusts the peripheral speed of the can roll 116 and a tension sensor roll that measures the tension of the long resin film 112. 122 and the free roll 123 which guides the long resin film 112 are arrange | positioned in this order.

  In the unwinding roll 111 and the winding roll 124, the tension balance of the long resin film 112 is maintained by torque control using a powder clutch or the like. Further, the long resin film 112 is unwound from the unwinding roll 111 and wound around the winding roll 14 by the rotation of the can roll 116 and the motor-driven front feed roll 115 and the rear feed roll 121 that rotate in conjunction with the rotation of the can roll 116. It has come to be taken.

  In the vicinity of the can roll 116, as a film forming means, at a position facing a conveyance path defined on the outer peripheral surface of the can roll 116 (a region where the long resin film 112 is wound around the outer peripheral surface of the can roll 116). Magnetron sputtering cathodes 117, 118, 119 and 120 on which sputtering targets are respectively mounted are arranged, and reactive gases containing water or the like as described above in the vicinity of these magnetron sputtering cathodes 117, 118, 119 and 120. Gas supply pipes 125, 126, 127, 128, 129, 130, 131, 132 for releasing a mixed gas of (oxygen gas) and process gas (argon gas or the like) are provided.

  Even when the metal layer is formed using the magnetron sputtering cathodes 119 and 120, the reactive gas (oxygen) is supplied from the gas supply pipes 129, 130, 131, and 132 provided in the vicinity of the magnetron sputtering cathodes 119 and 120. Gas) is not supplied, but process gas (argon gas or the like) is supplied.

  By the way, the laminated body film shown in FIG. 3 is manufactured as follows using the sputtering film-forming apparatus of FIG. 5 and FIG. First, a metal absorption layer 41 and a metal layer (sputtering layer) 42 are first formed on the transparent substrate (resin film) 40 shown in FIG. 1, and then the transparent substrate (resin film) is set in a sputtering film forming apparatus. After the correction, a metal absorption layer 43 and a metal layer (sputtering layer) 44 are formed on the transparent substrate (resin film) 40. Thereafter, metal layers (wet plating layers) 55 and 56 shown in FIG. 2 are further laminated by a wet plating method, and the second metal absorption layer 67 shown in FIG. In addition, after the transparent substrate (resin film) is set again in the sputtering film forming apparatus, the second metal absorption layer 68 is formed into a film.

(3-3) Reactive Sputtering When an oxide target is applied for the purpose of forming the metal absorption layer (metal oxide film), the film formation rate is slow as described above and is not suitable for mass production. For this reason, Patent Documents 1 and 2 employ reactive sputtering using an alloy target made of a CuNi alloy or the like and introducing a reactive gas (oxygen gas) into a vacuum chamber.

  By the way, the laminated body film obtained by carrying out the continuous sputtering film-forming to the elongate resin film using the sputtering film-forming apparatus shown in FIG.5 and FIG.6 is an etching liquid in the longitudinal direction of a elongate resin film as mentioned above. It was confirmed that the etching rate was different and the etching rate of the film formation start side laminate film was faster than that of the film formation end side laminate film, and this phenomenon was different from the etching rate of the metal absorption layer (metal oxide film). This is described in Patent Documents 1 and 2 above.

  The chemical composition (the chemical state of Ni) of the metal absorption layer (metal oxide film) formed by reactive sputtering using an alloy target made of CuNi alloy or the like is, according to Non-Patent Document 1, a reactive gas. When oxygen is introduced, it becomes a NiO film, and when moisture is introduced, it becomes a NiOOH film. Therefore, the crystal grains are fine, and the presence of NiOOH, which is a hydroxide, affects the etching properties of the metal absorption layer (metal oxide film). It is estimated that

  For this reason, in Patent Documents 1 and 2, water or hydrogen is included in the reactive gas (oxygen gas) to compensate for the amount of moisture in the vacuum chamber that decreases during film formation, and depending on the longitudinal direction of the long resin film. A method for solving the phenomenon of different etching rates has been proposed.

The following four methods are known as methods for controlling the reactive gas.
(3-3-1) A method for releasing a reactive gas at a constant flow rate.
(3-3-2) A method of releasing reactive gas so as to maintain a constant pressure.
(3-3-3) A method of releasing reactive gas (impedance control) so that the impedance of the sputtering cathode becomes constant.
(3-3-4) A method of releasing reactive gas (plasma emission control) so that the plasma intensity of sputtering is constant.

(4) Problems when using a conventional sputtering film forming apparatus (4-1) Conventional sputtering film forming apparatus When the metal absorption layer (metal oxide film) is formed by a reactive sputtering method, FIGS. The sputtering film forming apparatus shown in FIG.

  When a sputtering film forming apparatus in which an alloy target such as a CuNi alloy is mounted on the sputtering cathodes 17, 18, 117, 118 is used, and a metal absorption layer (metal oxide film) is continuously formed by a reactive sputtering method. The reactive gas (oxygen gas) containing water supplied from the gas supply pipes 25, 26, 27, 28, 125, 126, 127, and 128, along with the process gas (argon gas, etc.) Since it passes through the plasma region, particles such as hydroxide caused by reactive gas (oxygen gas) or water are easily deposited on the alloy target surface, and foreign matter called nodules is also generated. It becomes easy. Since these foreign substances called particles and nodules are insulators, there is a problem that particle deposits are shed by an abnormal discharge (arc discharge) due to charging, which hinders subsequent reactive sputtering. This was conspicuous when the input power (sputter power) or input current (sputter current) to the cathodes 17, 18, 117, and 118 was set high.

(5) Improvement Measures According to the Present Invention (5-1) In the reactive sputtering method of Patent Documents 1 and 2 using the sputtering film forming apparatus shown in FIGS. In consideration of the workability of the film, an alloy target made of CuNi alloy or the like having excellent etching properties is applied. However, as described above, oxidation of CuNi alloy by reactive sputtering is more dominant than Cu. It has been confirmed by the present inventors.

  When the metal absorption layer (metal oxide film) is formed using an alloy target composed of a CuNi alloy or the like and a reactive gas (oxygen gas), it is difficult to oxidize Cu, and the sputtering target is exposed to the sputtering cathode. Since it was necessary to set the input power (sputtering power) or the input current (sputtering current) high, it was confirmed that the accumulation of particles on the surface of the alloy target and the generation of foreign matter called nodules become prominent.

  Therefore, in the present invention, instead of the conventional reactive sputtering method using an alloy target made of a CuNi alloy or the like, the reactive multiple divided into “Cu target” and “addition metal (for example, Ni) target” other than Cu. By adopting the sputtering film forming method, the above problem is solved.

That is, the present invention
A cooling can roll that conveys a long body in contact with the surface, and a plurality of sputtering film forming means arranged opposite to the surface of the cooling can roll are provided in a vacuum chamber, and the sputtering film forming means In the sputtering film forming apparatus in which a thin film is formed on the surface of the elongated body conveyed through the gap with the cooling can roll, and at least one of the sputtering film forming means is constituted by a reactive multi-source sputtering film forming means,
The reactive multi-source sputtering film forming means is accommodated in the cathode box opened on the cooling can roll side, the first cathode chamber and the second cathode chamber partitioned by the partition plate in the cathode box, and the first cathode chamber. And a second sputtering cathode housed in the first sputtering cathode and the second cathode chamber to which the first target is mounted and a second target is mounted, a gas supply means for supplying a process gas into the first cathode chamber, and A gas supply means for supplying a process gas containing a reactive gas in the second cathode chamber;
Reactive multi-source sputtering film formation is performed by merging the first target particles flying from the first cathode chamber and the second target particles flying from the second cathode chamber in the space region in the tip direction of the partition plate and in the vicinity of the cooling can roll. It is made to be made.

(5-2) Sputtering film forming apparatus according to the present invention A long body (long resin film or the like) has two sets of reactive multiples on one side of the first metal absorption layer (metal oxide film) in the laminate film. The sputtering film forming apparatus according to the present invention will be described by taking as an example the case of forming a film using the sputtering film forming means.

  FIG. 7 is a partially enlarged view of a sputtering film forming apparatus according to the present invention. A can roll (cooling can roll) 200, a first film forming means 1A disposed opposite to the surface of the can roll 200, A film means 2A, a third film forming means 3A, and a fourth film forming means 4A are shown. In FIG. 7, the structure upstream of the front feed roll 220 and the structure downstream of the rear feed roll 320 are not shown, but the unwinding roll 11 to the front feed roll 15 of the sputtering film forming apparatus shown in FIG. And the structure from the rear feed roll 21 to the take-up roll 24 is the same. Further, the first film forming means 1A and the second film forming means 2A shown in FIG. 7 correspond to the two sets of reactive multi-source sputtering film forming means.

  That is, the first film forming means 1A includes a cathode box 212 having an open can roll 200 side, a first cathode chamber 601 and a second cathode chamber 602 partitioned by a partition plate 214 in the cathode box 212, and the first A cylindrical first magnetron sputtering cathode 202, which is accommodated in one cathode chamber 601 and mounted with a first rotary target (Cu target) (not shown), and a second rotary target (not shown) accommodated in a second cathode chamber 602. A cylindrical second magnetron sputtering cathode 203 to which (addition metal Ni target) is mounted, a process gas supply pipe 206 for supplying process gas (for example, argon gas) into the first cathode chamber 601, and the first Reactive gas (oxygen) in the two cathode chambers A reactive gas supply pipe 208 for supplying a process gas containing water and an additive gas supply pipe 207 for supplying a process gas containing an aqueous additive gas (water or hydrogen), and the cathode box 212 In the vicinity of the can roll 200, a shielding mask comprising a pair of shielding plates 216 and 217 arranged with a gap serving as an opening is attached.

  Then, from the first rotary target (Cu target) particles flying from the first cathode chamber 601 and the second cathode chamber 602 in the space region near the can roll 200 in the distal direction of the partition plate 214 in the first film forming means 1A. The second rotary target (Ni target) particles that come in are combined and reacted with the reactive gas (oxygen gas) supplied from the second cathode chamber 602 (reactive multi-source sputtering), so that the length on the can roll 200 is increased. A metal absorption layer (metal oxide film) is formed on the surface of the long resin film 201.

  In addition, input power or input to the cylindrical first magnetron sputtering cathode 202 to which the first rotary target (Cu target) is attached and the cylindrical second magnetron sputtering cathode 203 to which the second rotary target (Ni target) is attached. The electric current is set to a numerical value at which a copper alloy thin film having a Ni mixing ratio of 3 to 40% as an additive metal is formed.

  The second film forming means 2A also includes the cathode box 213 opened on the can roll 200 side, the first cathode chamber 701 and the second cathode chamber 702 partitioned by the partition plate 215 in the cathode box 213, and the first A cylindrical first magnetron sputtering cathode 204, which is accommodated in one cathode chamber 701 and mounted with a first rotary target (Cu target) (not shown), and a second rotary target (not shown) accommodated in a second cathode chamber 702. A cylindrical second magnetron sputtering cathode 205 on which (a Ni target as an additive metal) is mounted, a process gas supply pipe 209 for supplying a process gas (for example, argon gas) into the first cathode chamber 701, and the first Reactive gas (oxygen gas) in the two cathode chambers A reactive gas supply pipe 211 for supplying a process gas containing water and an additive gas supply pipe 210 for supplying a process gas containing an aqueous additive gas (water or hydrogen), and a canister of the cathode box 213 In the vicinity of the roll 200, a shielding mask made up of a pair of shielding plates 218 and 219 arranged with a gap serving as an opening is attached.

  Then, from the first rotary target (Cu target) particles flying from the first cathode chamber 701 and the second cathode chamber 702 in the space region near the can roll 200 in the distal direction of the partition plate 215 in the second film forming means 2A. The surface of the long resin film 201 is formed by merging the second rotary target (Ni target) particles that come and reacting with the reactive gas (oxygen gas) supplied from the second cathode chamber 702 (reactive multi-source sputtering). A similar metal absorption layer (metal oxide film) is formed on the metal absorption layer (metal oxide film).

  In addition, input power or input to the cylindrical first magnetron sputtering cathode 204 on which the first rotary target (Cu target) is mounted and the cylindrical second magnetron sputtering cathode 205 on which the second rotary target (Ni target) is mounted. The current is also set to a value at which a copper alloy thin film is formed in which the Ni mixing ratio of the additive metal is 3 to 40%.

  According to the first film forming unit 1A and the second film forming unit 2A related to the reactive multi-source sputtering, the second rotary target (Ni target) that easily reacts with the reactive gas (oxygen gas) is formed into the cylindrical second. By attaching the first rotary target (Cu target), which is mounted on the magnetron sputtering cathodes 203 and 205 and the reactivity is inferior to that of the second rotary target (Ni target), to the cylindrical first magnetron sputtering cathodes 202 and 204, each sputtering is performed. The input power (or input current) to the cathode can be set to a value suitable for each target to be mounted, and the first cathode chamber 601 in which no additive gas (water or hydrogen) or reactive gas is supplied, In 701, the first rotary target (Cu target) It is possible to prevent generation of hydroxides such particles sediment to g) surface.

  That is, in the first cathode chamber in which the first rotary target (Cu target) that is the main component of the metal absorption layer (metal oxide film) is accommodated, the first cathode chamber is in a state close to an atmosphere of only normal process gas (for example, argon gas). Sputtering is performed while setting the input power (or input current) to one magnetron sputtering cathode to be high (however, the Ni mixing ratio of the additive metal is in the range of 3 to 40%), while the addition greatly contributes to absorption A reactive gas (oxygen gas) and an additive gas (water or hydrogen) are introduced into the second cathode chamber in which a second rotary target (Ni target), which is a metal for use, is housed, and the first cathode is subjected to reactive sputtering. Cu sputtered particles flying from chamber and Ni sputtered particles flying from second cathode chamber are long resin Reacts with Irumu surface to form a CuNi alloy metal absorbing layer is (metal oxide film). The second rotary target (Ni target) is reactive sputtering, but the input power (or input current) can be overwhelmingly lower than in the conventional method using an alloy target made of CuNi alloy. Since generation of particle deposits such as materials is suppressed, reactive sputtering does not become unstable in a short time, and waste of input power (or input current) is also eliminated.

  In addition, about the 1st rotary target (Cu target) with which the cylindrical 1st magnetron sputtering cathode 202, 204 is mounted, since deposition in the non-erosion area | region of particles, such as a hydroxide accompanying reactive sputtering, is suppressed, rotary. A plate-like target can be applied instead of the target. In addition, it is desirable that the inside of the cathode boxes 212 and 213 in the first film forming unit 1A and the second film forming unit 2A be differentially exhausted separately from the exhaust in the vacuum chamber.

  Next, FIG. 10 is an enlarged view of the cathode box 212 shown in FIG.

  That is, FIG. 10 shows a cylindrical first magnetron sputtering cathode 202 which is accommodated in the first cathode chamber 601 and on which a first rotary target (Cu target) (not shown) is mounted, and is accommodated in the second cathode chamber 602. A cylindrical second magnetron sputtering cathode 203 on which a second rotary target (Ni target as an additive metal) (not shown) is mounted is shown in an enlarged manner, and each cylindrical first magnetron sputtering cathode 202 and a cylindrical second magnet are shown. A plurality of magnets 611 and 612 are shown fixedly disposed within a rotating sleeve (not shown) of the magnetron sputtering cathode 203.

  Specifically, the plurality of magnets 611 and 612 are appropriately fixed in a rotating sleeve (not shown) of the cylindrical first magnetron sputtering cathode 202 and the cylindrical second magnetron sputtering cathode 203 (not shown). The normal line at the center of the surface of each of the magnets 611 and 612 facing the can roll 200 is a space area in the vicinity of the can roll 200 (area where the first rotary target particles and the second rotary target particles merge) The first rotary target particles and the second rotary target particles are held by the can roll 200 along the direction of each normal line indicated by an arrow in FIG. It is adjusted so that it can fly uniformly on the long resin film.

  Further, a shielding mask composed of a pair of shielding plates 216 and 217 disposed near the can roll 200 and through a gap serving as an opening, and the cylindrical first magnetron sputtering cathode 202 and the cylindrical second magnetron sputtering cathode 203 For each arrangement position, in consideration of the wraparound phenomenon of the first rotary target particles and the second rotary target particles from the shielding mask, when the angle of the tip of the partition plate 214 with respect to the bottom surface of the cathode box 212 is 90 degrees, The direction of the first rotary target particles flying from the cylindrical first magnetron sputtering cathode 202 and the cylindrical second magnetron sputtering cathode 203 and the direction of the second rotary target particles intersect with each other at an angle range of ± 30 degrees with respect to the 90-degree direction. In other words, may each target particles to fly from a direction of 60 degrees to 120 degrees) to adjust.

  Next, the third film forming means 3A and the fourth film forming means 4A provided on the downstream side of the first film forming means 1A and the second film forming means 2A are the first metal absorption layer (metal oxide film). ) On which a second metal layer (sputtering layer) is formed.

  Then, as shown in FIG. 7, the third film forming means 3A includes a cathode box 313 whose can roll 200 side is opened, and a cylinder which is accommodated in the cathode box 313 and on which a rotary target (Cu target) (not shown) is mounted. A magnetron sputtering cathode 304 and a process gas supply pipe 309 for supplying a process gas (for example, argon gas) into the cathode box 313, and an opening is formed in the vicinity of the can roll 200 of the cathode box 313. A shielding mask composed of a pair of shielding plates 318 and 319 disposed with a gap is provided.

  As shown in FIG. 7, the fourth film forming means 4A is also a cathode box 312 having an open can roll 200 side, and a cylinder that is accommodated in the cathode box 312 and on which a rotary target (Cu target) (not shown) is mounted. A magnetron sputtering cathode 302 and a process gas supply pipe 306 for supplying a process gas (for example, argon gas) into the cathode box 312, and an opening is provided in the vicinity of the can roll 200 of the cathode box 312. A shielding mask including a pair of shielding plates 316 and 317 arranged with a gap is provided.

  Then, on the first metal absorption layer (metal oxide film) formed by the first film formation means 1A and the second film formation means 2A, the third film formation means 3A and the fourth film formation means 4A A second metal layer (Cu sputtering layer) is formed.

  Although the Cu targets of the third film forming means 3A and the fourth film forming means 4A shown in FIG. 7 are composed of rotary targets, they are not reactive sputtering, so that plate targets (Cu (Target).

(5-3) Sputtering Film Forming Apparatus According to Comparative Example FIG. 9 is a partially enlarged view of a sputtering film forming apparatus according to a comparative example to which a conventional CuNi alloy (composition ratio 7: 3) target is applied. (Cooling can roll) 400 and a first film forming means 1a, a second film forming means 2a, a third film forming means 3a, and a fourth film forming means 4a arranged opposite to the surface of the can roll 400 are shown. . 9 does not show the structure upstream of the front feed roll 420 and the structure downstream of the rear feed roll 520, but the unwinding roll 11 to the front feed roll 15 of the sputtering film forming apparatus shown in FIG. And the structure from the rear feed roll 21 to the take-up roll 24 is the same. Further, a first metal absorbing layer (metal oxide film) is formed by the first film forming means 1a and the second film forming means 2a constituting the reactive sputtering means, and the third film forming means 3a and the fourth film forming means 2a. A second metal layer (sputtering layer) is formed by the film means 4a.

  First, as shown in FIG. 9, the first film forming means 1a is mounted with a cathode box 412 whose can roll 400 side is opened, and a rotary target (CuNi alloy target) which is accommodated in the cathode box 412 and which is not shown. A cylindrical magnetron sputtering cathode 402, a reactive gas supply pipe 406 for supplying a process gas (for example, argon gas) containing a reactive gas (oxygen gas) in the cathode box 412, and an aqueous additive gas (water or hydrogen) ), And a pair of shielding plates 416 and 417 disposed in the vicinity of the can roll 400 of the cathode box 412 via a gap serving as an opening. The shielding mask which consists of is attached. Similarly, as shown in FIG. 9, the second film forming means 2a is also equipped with a cathode box 413 with the can roll 400 side open, and a rotary target (CuNi alloy target) not shown in the figure, housed in the cathode box 413. A cylindrical magnetron sputtering cathode 404, a reactive gas supply pipe 409 for supplying a process gas (for example, argon gas) containing a reactive gas (oxygen gas) in the cathode box 413, and an aqueous additive gas (water or A pair of shielding plates 418 disposed in the vicinity of the can roll 400 of the cathode box 413 with a gap serving as an opening, provided with an additive gas supply pipe 410 for supplying a process gas containing hydrogen) A shielding mask consisting of 419 is attached. A first metal absorption layer (metal oxide film) is formed by the first film forming means 1a and the second film forming means 2a constituting the reactive sputtering means.

  Next, as shown in FIG. 9, the third film forming unit 3 a is mounted with a cathode box 513 with the can roll 400 opened, and a rotary target (Cu target) that is housed in the cathode box 513 and is not shown. A cylindrical magnetron sputtering cathode 504 and a process gas supply pipe 509 for supplying a process gas (for example, argon gas) into the cathode box 513 are provided, and an opening is provided near the can roll 400 of the cathode box 513. The shielding mask which consists of a pair of shielding board 518,519 arrange | positioned through the clearance gap which becomes is attached. Similarly, as shown in FIG. 9, the fourth film forming unit 4a is also equipped with a cathode box 512 with the can roll 400 open, and a rotary target (Cu target) that is housed in the cathode box 512 and not shown. A cylindrical magnetron sputtering cathode 502 and a process gas supply pipe 506 for supplying a process gas (for example, argon gas) into the cathode box 512 are provided, and an opening is provided near the can roll 400 of the cathode box 512. The shielding mask which consists of a pair of shielding board 516,517 arrange | positioned through the clearance gap which becomes is attached. Then, on the first metal absorption layer (metal oxide film) formed by the first film forming means 1a and the second film forming means 2b, the third film forming means 3a and the fourth film forming means 4a A second metal layer (Cu layer) is formed.

(6) Moisture pressure control The deposition of the metal absorption layer (metal oxide film) by the sputtering deposition apparatus according to the present invention may take several hours, and the moisture pressure in the vacuum chamber during that time is controlled. It is necessary to stabilize the set value. For this reason, the partial pressure of H ₂ O and Ar gas is measured using a quadrupole mass spectrometer, and the amount of water released (supply amount) is adjusted so that this ratio “H ₂ O / Ar” is constant. The total is controlled. FIG. 8 shows the water flow rate “H ₂ O flow rate” and the ratio “H ₂ O / Ar” during film formation. Here, the PID control is performed so that the ratio “H ₂ O / Ar” becomes 0.012.

From the graph of FIG. 8, it can be confirmed that the ratio “H ₂ O / Ar” during film formation is maintained at 0.012. Further, the water flow rate “H ₂ O flow rate” decreases with the start of film formation. This is because the temperature around the cathode and the inner wall of the vacuum chamber rises due to the thermal load of sputtering with the elapse of the sputtering time, so that water is released, so that the water flow rate for maintaining the ratio “H ₂ O / Ar” of 0.012 The “H ₂ O flow rate” is gradually decreasing. Later, the water flow rate “H ₂ O flow rate” increased.

Furthermore, the temperature around the cathode and the inner wall of the vacuum chamber increased due to the thermal load of sputtering with the elapse of the sputtering time, and the water had already separated, so that the ratio “H ₂ O / Ar” of 0.012 was maintained. The water flow rate “H ₂ O flow rate” is gradually increasing.

  Examples of the present invention will be specifically described below with reference to comparative examples.

[Example]
A sputtering film forming apparatus shown in FIG. 7 was used. The can roll 200 is made of stainless steel having a diameter of 800 mm and a width of 800 mm, and the surface of the roll body is hard chrome plated.

In the cathode boxes 212 and 213 forming the first metal absorption layer, cylindrical first magnetron sputtering cathodes 202 and 204 on which a first rotary target (Cu target) is mounted, and a second rotary target (Ni). Cylindrical second magnetron sputtering cathodes 203 and 205 on which a target) is mounted, process gas supply pipes 206 and 209 for supplying a process gas (argon gas), and a process gas including a reactive gas (O ₂ gas) Reactive gas supply pipes 208 and 211 to be supplied, and additive gas supply pipes 207 and 210 for supplying a process gas containing water addition gas are provided, and in the vicinity of the can roll 200 of each cathode box 212 and 213, Shielding plate 2 arranged through a gap serving as an opening The shielding mask made of 6,217,218,219 was attached.

  In the cathode boxes 312 and 313 forming the second metal layer, cylindrical magnetron sputtering cathodes 302 and 304 mounted with a rotary target (Cu target), and a process gas (argon) in the cathode boxes 312 and 313 are formed. Process gas supply pipes 306 and 309 for supplying gas), and shielding plates 316, 317, and 318 disposed in the vicinity of the can rolls 200 of the cathode boxes 312 and 313 through gaps serving as openings. A shielding mask consisting of 219 is attached.

  The moisture pressure and Ar partial pressure during film formation measure the atmosphere in the cathode boxes 212 and 213, and the process gas containing the water-added gas is introduced from the additive gas supply pipes 207 and 210 as described above. Also, the water pressure and Ar partial pressure during film formation were measured with a quadrupole mass spectrometer, and the water pressure and Ar when the water addition amount and feedback control were performed so that the water pressure and Ar partial pressure were 0.012. FIG. 8 shows the partial pressure ratio and the water flow rate.

  Sputtered at the cylindrical first magnetron sputtering cathodes 202 and 204 on which the first rotary target (Cu target) is mounted and on the cylindrical second magnetron sputtering cathodes 203 and 205 on which the second rotary target (Ni target) is mounted. The magnets 611 and 612 fixedly disposed in the rotating sleeves (not shown) of the magnetron sputtering cathodes 202, 204 and 203, 205 are attached to each other so that the particles come to the center of the opening of the shielding mask. (See FIG. 10).

The long resin film 201 was a PET film having a width of 600 mm and a length of 1000 m. While the can roll 200 was cooled to 0 ° C., the vacuum chamber was evacuated to 5 Pa by a plurality of dry pumps, and further evacuated to 3 × 10 ⁻³ Pa using a plurality of turbo molecular pumps and cryocoils. .

Then, 200 sccm of process gas (argon gas) is supplied from the process gas supply pipes 206 and 209 of the cathode boxes 212 and 213, 200 sccm of Ar gas and 40 sccm of O ₂ gas are supplied from the reactive gas supply pipes 208 and 211, and an additive gas supply pipe 207. , 210 to 10 sccm of Ar gas containing a water-added gas was introduced so that the water pressure and the Ar partial pressure were 0.012. In addition, 400 sccm of Ar gas was introduced from the process gas supply pipes 306 and 309 of the cathode boxes 312 and 313.

  After the conveyance speed of the long resin film 201 is 4 m / min, the composition ratio of Cu and Ni is 7: 3 as the first metal absorption layer, and the film thickness of the metal absorption layer is 20 nm. The first rotary target (Cu target) of the cathode boxes 212 and 213 is mounted on the cylindrical first magnetron sputtering cathodes 202 and 204, and the second rotary target (Ni target) is mounted. The input power to each cylindrical second magnetron sputtering cathode 203, 205 was set to about 1 kW. In addition, the metal (Cu) layer of the second layer is charged into cylindrical magnetron sputtering cathodes 302 and 304 equipped with rotary targets (Cu targets) in the cathode boxes 312 and 313 so that the film thickness is 80 nm. The power was set to about 8 kW.

  After the film formation was completed, the Cu and Ni composition ratio and film thickness of the metal absorption layer were measured. The composition ratio was 7: 3, the film thickness was 20 nm, and the metal layer thickness was 80 nm.

[Evaluation]
The average reflection in the visible wavelength region (400 to 700 nm) of the metal absorption layer measured through a long resin film using a self-recording spectrophotometer was 15%.

  Moreover, when the surface of the 2nd rotary target (Ni target) and the 1st rotary target (Cu target) which carried out reactive sputter | spatter aggressively by introduce | transducing reactive gas and water addition gas immediately is observed, an erosion edge part The generation of nodules and the deposition of reaction products were hardly observed including (at the end of the rotary target). The reason why there was almost no nodule generation and no reaction product deposition on the second rotary target (Ni target) was that the second rotary target (Ni target) was installed by applying reactive multi-component (binary) sputtering. Therefore, it is estimated that the influence of the sputtering film formation with a length of about 1000 m hardly occurred because the input power to the cylindrical second magnetron sputtering cathodes 203 and 205 was as small as 1 kW (it was low).

  Even when nodule generation or reaction products accumulate on the second rotary target (Ni target) mounted on each cylindrical second magnetron sputtering cathode 203, 205, the supply of reactive gas is stopped. It is known that the second rotary target (Ni target) can be cleaned by performing pre-sputtering or post-sputtering on the two rotary targets (Ni target).

[Comparative example]
A sputtering film forming apparatus according to a comparative example shown in FIG. 9 was used. The can roll 400 is made of stainless steel having a diameter of 800 mm and a width of 800 mm, and the surface of the roll body is hard chrome plated.

In the cathode boxes 412 and 413 forming the first metal absorption layer, cylindrical magnetron sputtering cathodes 402 and 404 on which a Cu—Ni alloy (composition ratio 7: 3) rotary target is mounted, and a reactive gas Reactive gas supply pipes 406 and 409 for supplying process gas (argon gas) containing (O ₂ gas), and additive gas supply pipes 407 and 410 for supplying process gas containing water added gas are provided, and In the vicinity of the can roll 400 of each of the cathode boxes 412, 413, a shielding mask made up of shielding plates 416, 417, 418, 419 arranged with a gap serving as an opening is provided.

  In the cathode boxes 512 and 513 forming the second metal layer, cylindrical magnetron sputtering cathodes 502 and 504 mounted with a rotary target (Cu target), and in the cathode boxes 512 and 513, a process gas (argon) Process gas supply pipes 506 and 509 for supplying gas), and shielding plates 516, 517, and 518 disposed in the vicinity of the can roll 400 of the cathode boxes 512 and 513 through gaps serving as openings. A shielding mask consisting of 519 was attached.

  The moisture pressure and Ar partial pressure during film formation measure the atmosphere in the cathode boxes 412, 413, and the process gas containing the water addition gas is introduced from the addition gas supply pipes 407, 410 as described above. Also, the water pressure and Ar partial pressure during film formation were measured with a quadrupole mass spectrometer, and the water pressure and Ar when the water addition amount and feedback control were performed so that the water pressure and Ar partial pressure were 0.012. FIG. 8 shows the partial pressure ratio and the water flow rate.

The long resin film 401 was a PET film having a width of 600 mm and a length of 1000 m. While controlling the can roll 400 at 0 ° C., the vacuum chamber was evacuated to 5 Pa by a plurality of dry pumps, and further evacuated to 3 × 10 ⁻³ Pa using a plurality of turbo molecular pumps and cryocoils. .

Then, 400 sccm of Ar gas and 40 sccm of O ₂ gas are supplied from the reactive gas supply pipes 406 and 409 of the cathode boxes 412 and 413, and the moisture pressure and Ar partial pressure are 0.012 from the additive gas supply pipes 407 and 410. Ar gas containing water addition gas was introduced at 10 to 15 sccm. Further, 400 sccm of Ar gas was introduced from the process gas supply pipes 506 and 509 of the cathode boxes 512 and 513.

  After the conveying speed of the long resin film 401 is 4 m / min, the Cu—Ni alloy (composition ratio 7: 3) of the cathode boxes 412 and 413 is set so that the thickness of the metal absorption layer in the first layer is 20 nm. ) The input power to the cylindrical magnetron sputtering cathodes 402 and 404 on which the rotary target is mounted was set to about 3 kW. In addition, the metal (Cu) layer of the second layer is charged into the cylindrical magnetron sputtering cathodes 502 and 504 on which the rotary targets (Cu targets) in the cathode boxes 512 and 513 are mounted so that the film thickness becomes 80 nm. The power was set to about 8 kW.

  After completion of the film formation, the metal absorption layer had a thickness of 20 nm and the metal layer had a thickness of 80 nm.

[Evaluation]
The average reflection in the visible wavelength region (400 to 700 nm) of the metal absorption layer measured through a long resin film using a self-recording spectrophotometer was 15%.

  In addition, when the surface of a Cu—Ni alloy (composition ratio 7: 3) rotary target that was actively subjected to reactive sputtering by introducing a reactive gas and a water-added gas most recently was observed, nodules were found near the erosion edge. Generation | occurrence | production and deposition of the reaction product were confirmed, and when the sputtering film-forming apparatus which concerns on a comparative example was used, it turned out that it is inferior to film-forming stability compared with the sputtering film-forming apparatus which concerns on an Example.

  In addition, when the etching property of the laminated film (metal layer / metal absorption layer) using a ferric chloride aqueous solution as an etching solution was evaluated, there was no significant difference between Examples and Comparative Examples.

  According to the method of the present invention, the surface of the rotary target can be maintained in a clean state for a long time, so that an abnormal discharge due to nodules and deposits is suppressed, and a thin film to which foreign matter or the like does not adhere can be formed. For this reason, it has the industrial possibility utilized for manufacture of the laminated body film used for the material of the electrode substrate film for touch panels installed in the surface of FPD (flat panel display).

40, 50, 60, 70 Transparent substrate (resin film)
41, 43, 51, 53, 61, 63 Metal absorption film 67, 68, 77, 78 Second metal absorption film 42, 44, 52, 54, 62, 64, 72, 74 Metal layer (sputtering layer)
55, 56, 65, 66, 75, 76 Metal layer (wet plating layer)
10 Vacuum chamber 11 Unwinding roll 12 Long resin film (long body)
13 Free roll 14 Tension sensor roll 15 Front feed roll 16 Can roll 17, 18, 19, 20 Magnetron sputtering cathode 21 Rear feed roll 22 Tension sensor roll 23 Free roll 24 Winding rolls 25, 26, 27, 28, 29, 30 , 31, 32 Gas supply pipe 110 Vacuum chamber 111 Unwind roll 112 Long resin film 113 Free roll 114 Tension sensor roll 115 Front feed roll 116 Can roll 117, 118, 119, 120 Magnetron sputtering cathode 121 Rear feed roll 122 Tension sensor Roll 123 Free roll 124 Winding rolls 125, 126, 127, 128, 129, 130, 131, 132 Gas supply pipes 1A, 1a First film forming means 2 , 2a Second film forming means 3A, 3a Third film forming means 4A, 4a Fourth film forming means 200 Can roll 201 Long resin films 202, 204 First magnetron sputtering cathode 203, 205 Second magnetron sputtering cathodes 302, 304 Magnetron sputtering cathodes 206, 209, 306, 309 Process gas supply pipes 207, 210 Addition gas supply pipes 208, 211 Reactive gas supply pipes 212, 213, 312, 313 Cathode box 214, 215 Partition plates 216, 217, 218, 219 316, 317, 318, 319 Shield plate 220, 420 Front feed roll 320, 520 Rear feed roll 400 Can roll 401 Long resin film 402, 404, 502, 504 Magnetrons Attering cathode 406, 409 reactive gas supply pipe 407, 410 additive gas supply pipe 506, 509 process gas supply pipe 412, 413, 512, 513 cathode box 416, 417, 418, 419, 516, 517, 518, 519 shielding Plates 601 and 701 First cathode chamber 602 and 702 Second cathode chamber 611 and 612 Magnet

Claims (14)

A cooling can roll that conveys a long body in contact with the surface, and a plurality of sputtering film forming means arranged opposite to the surface of the cooling can roll are provided in a vacuum chamber, and the sputtering film forming means In the sputtering film forming apparatus in which a thin film is formed on the surface of the elongated body conveyed through the gap with the cooling can roll, and at least one of the sputtering film forming means is constituted by a reactive multi-source sputtering film forming means,
The reactive multi-source sputtering film forming means is accommodated in the cathode box opened on the cooling can roll side, the first cathode chamber and the second cathode chamber partitioned by the partition plate in the cathode box, and the first cathode chamber. And a second sputtering cathode housed in the first sputtering cathode and the second cathode chamber to which the first target is mounted and a second target is mounted, a gas supply means for supplying a process gas into the first cathode chamber, and A first target that is provided with a gas supply means for supplying a process gas containing a reactive gas in the second cathode chamber and that comes from the first cathode chamber in the space region in the direction of the tip of the partition plate and in the vicinity of the cooling can roll. Combine the particles and the second target particles flying from the second cathode chamber Sputtering apparatus, wherein a reactive multi-source sputtering deposition is performed.   The first sputtering cathode and the second sputtering cathode are constituted by a magnetron sputtering cathode in which a plurality of magnets are fixedly arranged, and the normal line at the center of the surface of each magnet facing the cooling can roll is a cooling can. The sputtering film forming apparatus according to claim 1, wherein the sputtering film forming apparatus intersects at a substantially central portion of the space region in the vicinity of the roll.   3. The sputtering film formation according to claim 1, wherein the second sputtering cathode on which the second target is mounted is constituted by a cylindrical magnetron sputtering cathode, and the second target is constituted by a rotary target. apparatus.   2. The shielding mask having an opening is disposed near the cooling can roll of the cathode box, and the opening of the shielding mask is aligned with the space area near the cooling can roll. The sputtering film-forming apparatus described in 1. The long body is transported while being held in contact with the surface of the cooling can roll provided in the vacuum chamber, and a thin film is formed on the surface of the long body by a plurality of sputtering film forming means arranged to face the cooling can roll surface. In a sputtering film forming method comprising: forming and forming at least one of the sputtering film forming means by a reactive multi-source sputtering film forming means;
The reactive multi-source sputtering film forming means is accommodated in the cathode box opened on the cooling can roll side, the first cathode chamber and the second cathode chamber partitioned by the partition plate in the cathode box, and the first cathode chamber. And a second sputtering cathode housed in the first sputtering cathode and the second cathode chamber to which the first target is mounted and a second target is mounted, a gas supply means for supplying a process gas into the first cathode chamber, and A first target that is provided with a gas supply means for supplying a process gas containing a reactive gas in the second cathode chamber and that comes from the first cathode chamber in the space region in the direction of the tip of the partition plate and in the vicinity of the cooling can roll. Combine the particles and the second target particles flying from the second cathode chamber Sputtering method and performing a reactive multi-source sputtering deposition.   The first sputtering cathode and the second sputtering cathode are configured by a magnetron sputtering cathode in which a plurality of magnets are fixedly arranged, and the normal line at the center of the surface of each magnet facing the cooling can roll is a cooling can. 6. The sputtering film forming method according to claim 5, wherein the layers intersect at a substantially central portion of the space region in the vicinity of the roll.   The sputtering film formation according to claim 5 or 6, wherein the second sputtering cathode on which the second target is mounted is constituted by a cylindrical magnetron sputtering cathode, and the second target is constituted by a rotary target. Method.   6. The sputtering film forming method according to claim 5, wherein the reactive gas is oxygen gas or nitrogen gas.   The sputtering film forming method according to claim 5 or 8, wherein the reactive gas is composed of oxygen gas, and the reactive gas contains water or hydrogen.   The first target accommodated in the first cathode chamber is constituted by a copper target, and the second target accommodated in the second cathode chamber is constituted by a metal target for addition other than copper. Sputtering film forming method.   The additive metal target is composed of one or more metals selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Mn, Ni, Co, and Zn. 10. The sputtering film forming method according to 10.   The copper alloy thin film in which the mixing ratio of the additive metal to copper is 3 to 40% is formed by adjusting the input power or input current to the first sputtering cathode and the second sputtering cathode. The sputtering film-forming method of 11. It is composed of a long body made of a transparent resin film and a laminated film formed on at least one side of the long body, and the laminated film is a first metal absorption layer counted from the long body side, In the manufacturing method of the laminated body film which has the copper layer of the 2nd layer and the metal absorption layer of the 3rd layer,
A method for producing a laminate film, wherein the first metal absorption layer and the third metal absorption layer are formed by the sputtering film forming method according to claim 5.   14. The method for producing a laminate film according to claim 13, wherein the film thicknesses of the first metal absorption layer and the third metal absorption layer are set in a range of 15 nm to 30 nm.